EP0440520A1 - Verfahren zur Herstellung von Polycarbosilanen in Gegenwart von geschmolzenem Natriummetall und Komplexbildnern - Google Patents

Verfahren zur Herstellung von Polycarbosilanen in Gegenwart von geschmolzenem Natriummetall und Komplexbildnern Download PDF

Info

Publication number
EP0440520A1
EP0440520A1 EP91400125A EP91400125A EP0440520A1 EP 0440520 A1 EP0440520 A1 EP 0440520A1 EP 91400125 A EP91400125 A EP 91400125A EP 91400125 A EP91400125 A EP 91400125A EP 0440520 A1 EP0440520 A1 EP 0440520A1
Authority
EP
European Patent Office
Prior art keywords
radical
formula
process according
chr5
moles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91400125A
Other languages
English (en)
French (fr)
Inventor
Pierre Ardaud
Maurice Charpenel
Gérard Mignani
Gérard Soula
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0440520A1 publication Critical patent/EP0440520A1/de
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to a process for the preparation of polycarbosilanes by reacting different specific halogenosilanes monomers in the presence of molten metallic sodium and sequestering agents.
  • non-hydrogenated monomeric halosilanes optionally carrying ethylenic groups are placed in the presence of alkali metal, and more particularly potassium due to its high reactivity on halosilanes and its low melting temperature compared to other alkali metals, such as in particular sodium, lithium.
  • halogenosilanes monomers which are optionally carrying ethylenic groups are reacted in the presence of an alkali metal, and more particularly potassium, sodium or a mixture of the two. .
  • the polymer obtained, according to EP-B-0 123 934 which preferably uses sodium is a polysilane while that obtained, according to EP-B-0 123 162, which preferably uses potassium, is rather a polycarbosilane.
  • Patent application DE-A-3 841 598 describes a process for the preparation of polysilanes by reacting dihalosilanes with sodium in the presence of crown ether.
  • the silanes introduced do not carry vinyl radicals (see the examples) and, consequently, the polysilanes obtained can only be transformed into polycarbosilanes by a subsequent heating step which does not allow the structure of the polycarbosilane obtained to be controlled.
  • An object of the invention is to propose a process for the preparation of polycarbosilanes in one step.
  • Another object of the invention is to have the possibility of varying the crosslinking rate in the polycarbosilane obtained in a controlled manner.
  • Another object is to propose a process for the preparation of polycarbosilanes which is easy and economical to use and which makes it possible to homogenize and increase the molecular weights of the polymers obtained.
  • the present invention which in fact relates to a process for the preparation of polycarbosilanes by reaction of at least one of each of the two monomeric silanes of formulas: R1R2 SiCl2 R13SiCl in which R1, identical or different, represents the hydrogen atom or a hydrocarbon radical, R2 is the vinyl radical, process characterized in that it is carried out in the presence of sodium metal molten in an organic solvent and sequestering agents of such that the ratio r1 of the number of moles of sequestering agents to the number of moles of sodium is between 0.001 and 1 and preferably between 0.01 and 0.05.
  • the fact of coupling the sodium metal with at least one sequestering agent makes it possible to approach the high reactivity of the potassium metal with respect to vinylated monomeric silanes, while avoiding the drawbacks of potassium ; that is to say its difficult industrial implementation and its high cost.
  • the reaction time and / or the molar ratio r1 defined above the number of carbon atoms present in the chain of the polymer obtained is modified: the reactivity of the sodium metal-sequestering agents couple can be modulated at will between the reactivity of the sodium metal and that of the potassium metal.
  • the Applicant has been able to observe that, completely unexpectedly, the various polymers obtained by such a process had a glass transition temperature (Tg) which increased with the molar ratio r1 as defined above.
  • Tg glass transition temperature
  • r1 molar ratio
  • the sequestering agents are preferably chosen from the complexing compounds of formula: N - ⁇ - CHR3-CHR3-O (CHR3-CHR3-O) not - R4 ⁇ 3 in which n is an integer between 0 and 10 inclusive, identical or different R3 is chosen from a hydrogen atom and a C1-C4 and R4 alkyl radical is a radical chosen from a C1-C12 alkyl or cycloalkyl radical, an alkylphenyl or phenylalkyl radical in which the alkyl part is C1-C12.
  • the sequestering agents are also chosen from macrocyclic polyethers (also called crown ethers) having 15 to 30 atoms in their cycle and consisting of 4 to 10 -OX units in which X is either -CHR5-CHR5 or -CHR5-CHR5- C (R6) 2, R5 and R6 identical or different being a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, one of the X may be -CHR5-CHR5-C (R6) 2 when the units - OX include the group -O- (CHR5) 2.
  • macrocyclic polyethers also called crown ethers
  • R6 R5 and R6 identical or different being a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms
  • the sequestering agents are also chosen from nitrogen-containing cyclic compounds, called cyclams such as and preferably used, the compound 1,4,8,11-tetramethyl 1,4,8,11-tetraazacyclotetradecane, subsequently named compound (A), of formula:
  • a sequestering agent of formula (3) is used in which R3 represents a hydrogen atom or a methyl radical, R4 and n having the preceding meaning.
  • n is greater than or equal to 0 and less than or equal to 6 and for which R4 represents an alkyl radical having from 1 to 4 carbon atoms.
  • tris (dioxa-3,6 heptyl) amine is particularly preferred.
  • crown ethers are described in French patent 69/43 879 published under the number 2 026 481, among these there may be mentioned, as examples, the compounds of formulas:
  • the crown ether preferably used is "15 Crown 5": formula (a), because it is specific for the complexing of Na+ ions.
  • the process is carried out, with, as a third reagent, at least one chlorosilane monomer of general formula: (4) R1 H SiCl2, R1 having the meaning given previously.
  • the process is carried out with, as a fourth reagent, at least one chlorosilane monomer of general formula (7): R1R9 SiCl2, in which R1 has the meaning given previously, R9 identical or different represents an alkyl radical, a cycloalkyl radical, an aryl radical, such as the phenyl and naphthyl radical, an arylalkyl or alkylaryl radical.
  • a chlorosilane monomer of the formula (7) is used in which R9 represents a C3-C6 alkyl radical, the cyclohexyl radical or the phenyl radical.
  • the ratio r2 corresponding to the number of moles of chlorosilanes of formula (1) over the number of moles of hydrogen chlorosilanes of formula (4), is between 0.5 and 4 and the ratio r3, corresponding to number of moles of monochlorosilanes introduced over the number of moles of dichlorosilanes introduced is between 0.2 and 0.8 approximately.
  • Monochlorosilanes correspond to monomeric chlorosilanes having, per molecule, a chlorine atom linked to the silicon atom, such as those of formula (2).
  • the dichlorosilanes correspond to the chlorosilane monomers having, per molecule, two chlorine atoms linked to the silicon atom, such as those of formulas (1), (4) and (7).
  • R1 in each of the formulas of the monomeric chlorosilanes introduced represents the methyl radical.
  • the sodium metal is preferably in slight molar excess (1 to 10% in molar excess) relative to the chlorosilane groups so that all of the chlorine atoms present in the monomeric silanes react.
  • the sodium metal is introduced into the reaction in various forms, such as for example, and without limitation: cylinder powder, tablet, piece, wire. After fusion, the molten sodium is in the form of fine droplets.
  • the reaction temperature must be maintained, for a period which can range from a few minutes to several hours, above the melting temperature of the sodium metal (that is to say 98 ° C.) and, preferably, maintained at the reflux temperature of the solvent used.
  • the reaction temperature can therefore be modified depending on the solvent used.
  • the solvent used must be aprotic and apolar, such as, for example: toluene, xylene and benzene, as well as their mixture.
  • the solvent used preferably, is toluene.
  • the polycarbosilane is separated from the reaction medium, and this by any means known per se, such as in particular by filtration.
  • the cooled reaction mixture mainly containing polycarbosilane, residual sodium, sequestering agents, sodium chloride and the solvent, is filtered.
  • the solid phase obtained is treated by adding water or alcohol to oxidize the residual sodium.
  • the solution of this phase is washed with water and then filtered.
  • the polymers according to the invention are fusible and soluble in most of the usual organic solvents, which can be very advantageous in terms of their formability.
  • the polymer obtained is pyrolyzed in an inert or reducing atmosphere or under vacuum at a temperature ranging from 100 ° C. to 2000 ° C. until the polymer is converted into a carbide-based ceramic. or silicon carbonitride, the ceramic based on silicon carbonitride being obtained by pyrolysis under an ammonia atmosphere of the polymer obtained by the process which is the subject of the present invention.
  • the polymer, before pyrolysis, can also be shaped, by molding or by spinning for example, to finally lead to the most diverse configurations such as filaments, fibers, molded articles, support coatings and others.
  • the polymer is spun by means of a conventional die (after possible melting if the polymer is initially in the solid state), then is heat treated at a temperature ranging from 100 ° C at 2000 ° C under vacuum or under an inert or reducing atmosphere, to give a ceramic fiber.
  • Me is the methyl radical
  • Vi is the vinyl radical
  • ⁇ is the phenyl radical
  • nBu is the radical n.butyle
  • M n is the number average molecular mass
  • M w is the weight average molecular mass
  • Ip is the polydispersity index
  • GPC gel permeation chromatography (polystyrene calibration).
  • Tg glass transition temperature (degree celsius) is obtained by the experiment of the fiber pendulum.
  • a 170 g mixture is introduced into a 1 liter glass reactor, maintained under an inert atmosphere (N2), equipped with mechanical stirring, a water cooler, a thermometer and heated by an oil bath.
  • 1.78 mol of sodium (41 g) previously cut into small pieces and washed several times with dry toluene, is added to the reactor. Agitation is increased during the melting of the sodium to ensure good dispersion of the metal in the form of fine droplets, then the following mixture is added to the solvent at reflux: the speed of addition is low because of the high exothermicity of the reaction (duration of addition: 2 hours for 125 ml of chlorosilanes).
  • reaction mixture is left under reflux for 2 hours then cooled and filtered under an inert atmosphere.
  • the precipitate is washed with 200 ml of toluene and the filtrate is washed twice with 25 ml of water then decanted and dried over MgSO4.
  • 16.2 g of polymer are obtained, which is in the form of a semi-solid oil.
  • r′2 defined in examples 2 to 4, is equal to 0.52.
  • r′2 defined in examples 2 to 4, is equal to 0.52.
  • r′2 defined in examples 2 to 4, is equal to 2.90.
  • reaction mixture is left under reflux for 4 hours, then cooled and filtered under an inert atmosphere.
  • the precipitate is washed with 200 ml of toluene and the filtrate is washed twice with water, then decanted is dried over MgSO4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Silicon Polymers (AREA)
EP91400125A 1990-02-01 1991-01-21 Verfahren zur Herstellung von Polycarbosilanen in Gegenwart von geschmolzenem Natriummetall und Komplexbildnern Withdrawn EP0440520A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9001383 1990-02-01
FR9001383A FR2657614A1 (fr) 1990-02-01 1990-02-01 Procede de preparation de polycarbosilanes en presence de sodium metallique fondu et d'agents sequestrants.

Publications (1)

Publication Number Publication Date
EP0440520A1 true EP0440520A1 (de) 1991-08-07

Family

ID=9393445

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91400125A Withdrawn EP0440520A1 (de) 1990-02-01 1991-01-21 Verfahren zur Herstellung von Polycarbosilanen in Gegenwart von geschmolzenem Natriummetall und Komplexbildnern

Country Status (3)

Country Link
EP (1) EP0440520A1 (de)
JP (1) JPH05320351A (de)
FR (1) FR2657614A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107698616A (zh) * 2017-12-05 2018-02-16 扬州三友合成化工有限公司 一种1，4‑双（二甲基硅烷基）苯的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023187A1 (de) * 1979-07-18 1981-01-28 Rhone-Poulenc Specialites Chimiques Verfahren zum Kondensieren von Hydroxysilylgruppen enthaltenden Polysiloxanen in Gegenwart von Alkali- oder Erdalkalimetallen und polyheteromacropolycyclische Verbindung
US4396796A (en) * 1980-10-30 1983-08-02 Western Electric Company, Inc. Encapsulated electronic devices and encapsulating compositions
EP0123934A1 (de) * 1983-03-31 1984-11-07 Union Carbide Corporation Olefinische Gruppierungen enthaltende Polysilanvorläufer für Siliciumcarbid
EP0180527A1 (de) * 1984-10-15 1986-05-07 Rhone-Poulenc Chimie Polykondensation von Hydroxysilylgruppen enthaltenden Polysiloxanen in Anwesenheit von Alkali- oder Erdalkalimetallen und eines Trioxyalkylalkylamins
EP0300862A2 (de) * 1987-07-10 1989-01-25 Rhone-Poulenc Chimie Polycarbosilanzusammensetzung, Verfahren zur Herstellung und Anwendung zur Herstellung von Siliciumkarbid-Gegenständen
DE3841598A1 (de) * 1987-12-11 1989-06-22 Nippon Telegraph & Telephone Verfahren zur herstellung von organometallischen hochpolymeren
EP0382651A1 (de) * 1989-01-23 1990-08-16 Rhone-Poulenc Chimie Verfahren zur Herstellung von Polysilanen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5293718A (en) * 1976-01-31 1977-08-06 Shin Etsu Chem Co Ltd Preparation of organosilicon compounds

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023187A1 (de) * 1979-07-18 1981-01-28 Rhone-Poulenc Specialites Chimiques Verfahren zum Kondensieren von Hydroxysilylgruppen enthaltenden Polysiloxanen in Gegenwart von Alkali- oder Erdalkalimetallen und polyheteromacropolycyclische Verbindung
US4396796A (en) * 1980-10-30 1983-08-02 Western Electric Company, Inc. Encapsulated electronic devices and encapsulating compositions
EP0123934A1 (de) * 1983-03-31 1984-11-07 Union Carbide Corporation Olefinische Gruppierungen enthaltende Polysilanvorläufer für Siliciumcarbid
EP0180527A1 (de) * 1984-10-15 1986-05-07 Rhone-Poulenc Chimie Polykondensation von Hydroxysilylgruppen enthaltenden Polysiloxanen in Anwesenheit von Alkali- oder Erdalkalimetallen und eines Trioxyalkylalkylamins
EP0300862A2 (de) * 1987-07-10 1989-01-25 Rhone-Poulenc Chimie Polycarbosilanzusammensetzung, Verfahren zur Herstellung und Anwendung zur Herstellung von Siliciumkarbid-Gegenständen
DE3841598A1 (de) * 1987-12-11 1989-06-22 Nippon Telegraph & Telephone Verfahren zur herstellung von organometallischen hochpolymeren
EP0382651A1 (de) * 1989-01-23 1990-08-16 Rhone-Poulenc Chimie Verfahren zur Herstellung von Polysilanen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WPI, FILE SUPPLIER accession nØ 77-66045y, Derwent Publications Ltd., Londres, GB; & JP-A-52 093718 (SHINETSU CHEM. IND. K.K.) 06-08-1977 *

Also Published As

Publication number Publication date
FR2657614A1 (fr) 1991-08-02
JPH05320351A (ja) 1993-12-03

Similar Documents

Publication Publication Date Title
EP0235486B1 (de) Zweistufenverfahren zur Herstellung von verknüpften Organopolysilazanen mit verbesserten Hitzeeigenschaften und deren Anwendung in der Herstellung von keramischen Materialien
EP0202170B1 (de) Polysilazanzusammensetzung, die durch Hydrosilylierung in Anwesenheit eines Metalls oder einer Metallverbindung vernetzt wird
EP0197863B1 (de) Verfahren zur Herstellung von Organopolysilazanen und Organopoly(disilyl)silazanen mit erhöhter Hitzestabilität und deren Anwendung für die Herstellung von keramischen Materialien
EP0209472B1 (de) Verfahren zur Hitzebehandlung von SiNH-, SiH und ungesättigten Gruppen enthaltenden Polysilazaten
EP0364323B1 (de) Verfahren zur Herstellung von Bor und Stickstoff enthaltenden Polymeren, die Bornitridvorläufer sind und die erhaltenen Produkte
EP0202177A1 (de) Mit Energie vernetzbare, freie radikalformende Verbindungen enthaltende Polysilazanzusammensetzungen
EP0327773B1 (de) Polysiloxazane, Verfahren zu deren Herstellung und deren Anwendung als Vorläufer für keramische Materialien
EP0208630B1 (de) Verfahren zur Behandlung eines mindestens zwei SiH-Gruppen enthaltenden Polysilazans mit einem kationischen Katalysator
EP0202176B1 (de) Verfahren zur Behandlung von Polyorganosilazanen und/oder Polyorganodisilylsilazanen mit einem ein ionisches mineralisches Salz und einen Komplexbildner enthaltenden Katalysator
EP0790964B1 (de) Verfahren zur herstellung keramischer materialien auf siliciumkarbidbasis und ausgangszusammensetzung für dieses verfahren
EP0235485A1 (de) Verfahren zur katalytischen Modifizierung eines Polysilazanes, das mindestens zwei aliphatisch ungesättigte Gruppen pro Molekül enthält
EP0373059B1 (de) Zusammensetzungen von Ausgangsmaterialien für Keramik auf Polysilazanbasis und durch Pyrolyse dieser Zusammensetzungen erhaltene Keramik
EP0440520A1 (de) Verfahren zur Herstellung von Polycarbosilanen in Gegenwart von geschmolzenem Natriummetall und Komplexbildnern
FR2745563A1 (fr) Procede pour la preparation d'oxynitrures de silicium et de bore, les oxynitrures obtenus, les polybrorsiloxanes obtenus comme intermediaire de synthese
EP0384857B1 (de) Verfahren zur Herstellung von Bornitrid
EP0351262A1 (de) Polysilazane, ihre Herstellung und Anwendung zur Herstellung von keramischen Materialien und die keramischen Materialien
EP0453350A1 (de) Verfahren zum Vernetzen von Bor und Stickstoff enthaltenden Polymeren und daraus hergestellte keramische Fasern
EP0415855A1 (de) Auf Bor, Stickstoff und Silizium basierende präkeramische Organometallverbindung
EP0448432A1 (de) Verfahren zur Herstellung keramischer Beschichtungen von Kohlesubstraten
EP0392941A1 (de) Verwendung von auf Bor und Stickstoff basierenden Polymeren als Vorläufer für auf Bornitrid basierenden keramischen Materialien und so erhaltene keramische Produkte
FR2693204A1 (fr) Procédé de préparation en milieu solvant de polysilylhydrazines.
FR2637902A1 (fr) Procede pour controler la polymerisation catalytique de compositions polysilazanes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19911228

K1C2 Correction of patent application (partial reprint) published

Effective date: 19910807

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19930803